SEPARATION PROCESS 2

SMJC 3283
Dr Khairunnisa binti Mohd. Paad
13 APRIL 2020 MONDAY
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CLASS ARRANGEMENTS
 MONDAY
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ATTENDANCE
GOOGLE FORMS
CRYSTALLIZATION
Part 2
 CHAPTER OBJECTIVES

•Ability to describe the basic principles

and applications of crystallization process
(continuation from last week).

•Calculation
THEORIES AND MECHANISM
OF CRYSTALLIZATION
 FORMATION OF CRYSTAL FROM
SOLUTION
• Supersaturation

• Nucleus formation

• Crystal growth
•
 CRYTALLIZATION PRINCIPLES
• The supersaturation must be above the a
certain value before nucleation will begin.
• Metastable region : the supersaturation is low
that nucleation will not start.
• Once the supersaturation has been raised
enough to be in the labile region, nucleation
can begin.
• At this point, crystals begin to grow, and the
supersaturation decreases.
• If the supersaturation becomes too high, the
nucleation rate will be too great, and
amorphous precipitate will result.

Typical phase diagram. The components in solution

consist of the product (ordinate) and the precipitating
reagent (abscissa). The lines with arrows out line one
possible way of performing the crystallization.
• Description: A supersaturated solution of
sodium acetate is crystallized by pouring it
onto a seed crystal, forming a stalagmite-like
solid. Heat is radiated from the solid.

• Shakhashiri, B.Z. Chemical Demonstrations: A Handbook for Teachers of

Chemistry
 SUPERSATURATION
• When the concentration of a compound in its solution is
greater than the saturation solubility of that compound in
that solvent the condition is known as supersaturation.
• This is an unstable state. From this supersaturates solution
the excess compound may be precipitated out or
crystallize. Supersaturation can be achieved by the
following methods:
1. Evaporation of solvent from the solution.
2. Cooling of the solution.
3. Formation of new solute molecule as a result of
chemical reaction 4. Addition of a substance, which is
more soluble in solvent than the solid to be crystallized.
 Supersaturation

Precipitation zone

Protein concentration
Phase
diagrams Nucleation zone

Metastable zone
Solubility Crystals grow, but
curve Nuclei form only
infinitely slowly
Under-saturation
(protein remains soluble; crystals dissolve)

Precipitant concentration (salt, PEG etc.)

REPRESENTATIVE
SOLUBILITY-
SUPERSOLUBILITY
DIAGRAM
• Point a
- The solution is undersaturated and crystals of all sizes dissolved.
• Point b
- Equilibrium exists between a saturated solution and crystal can be seen by naked
eye.
• Point c and point e
- Crystal can grow but cannot nucleate.
- Eg. Cloud at high altitude. (Contain tiny droplet of water but no seed crystals, do not
form crystal because temp below than freezing point.)
- Concentration on point c = the difference between the temperature at point e.
- The supersaturation (concentration) point c and b
∆𝑐 = 𝑐 − 𝑐%
• Point d and point f
- Point d: spontaneous nucleation of very small crystals (invisible to naked eye).
- Temperature difference between point d and f = The limiting supersaturation.

∆𝑐&'(') = 𝑐( − 𝑐%

- Relationship between solubility and crystal size (quantitate), Kelvin equation

, ./- 0-, 2 Describes the effect of droplet

𝑙𝑛 = diameter on vapor pressure and
,- /3456 solubility

vs= molar volume of crystals

𝜎S,L = interfacial tension
v = number of ions/ molecules of solute
c/cs = supersaturation ratio = S
 RELATIVE SUPERSATURATION
• Measured values of interfacial tension (surface energy) range
= 0.001 J/m2 for very soluble compounds to 0.170 for compounds of low
solubility.

• Relative supersaturation, s
𝑐 − 𝑐% 𝑐
𝑠= = −1= 𝑆−1
𝑐% 𝑐%
 NUCLEATION
• Nucleation refers to the birth of very small bodies of molecules from which the crystal
forms.
• In solution, solute molecules, ions or atoms remain in constant random motion. This is
due thermodynamic energy of the solution system.
• When the solute particles (molecules, atoms or ions) moves and collide over each
other they may form aggregates.
• This aggregates are called clusters. These are loose aggregates, which usually
disappear quickly.
• Some clusters may become so big that they may arrange themselves in lattice
arrangement. These bodies of aggregates are called embryo.
• However, embryos are unstable and they may break into clusters again.
• Some embryo may grow to such a size that it remains in thermodynamic equilibrium
with the solution. They do not revert back to clusters. These bodies are called nucleus
(plural is nuclei).
 PRIMARY NUCLEATION
• The generation of ultramicroscopic particles in the
process of nucleation is the sum of contributions by
primary nucleation and secondary nucleation.
• Primary nucleation : occurs in the absence of
crystals, secondary nucleation: attributed to the
influence of existing crystals.
• Primary nucleation can be either homogeneous
(no foreign particles are present) or heterogeneous
(foreign particles present during heterogeneous
nucleation).
Rate of homogenous primary nucleation:
 SECONDARY NUCLEATION
• Two types of secondary nucleation : shear nucleation (occurs as a result of
fluid shear on growing crystal faces), contact nucleation ( happens
because of crystals colliding with each other and with the impeller and
other vessel internal surfaces.
• Rate of secondary nucleation in crystallization (corraletes to experimental
data) is the following:

B = rate of secondary nucleation

MT = mass of crystal per magma
N= agitation rate (e.g. rpm of impeller)
kN, b, j, r = determined from experiments of interest
 CRYTALLIZATION PRINCIPLES
• The supersaturation must be above the a
certain value before nucleation will begin.
• Metastable region : the supersaturation is low
that nucleation will not start.
• Once the supersaturation has been raised
enough to be in the labile region, nucleation
can begin.
• At this point, crystals begin to grow, and the
supersaturation decreases.
• If the supersaturation becomes too high, the
nucleation rate will be too great, and
amorphous precipitate will result.

Typical phase diagram. The components in solution

consist of the product (ordinate) and the precipitating
reagent (abscissa). The lines with arrows out line one
possible way of performing the crystallization.
•
 Supersaturation

Precipitation zone

Protein concentration
Nucleation zone
Phase
diagrams Solubility
Metastable zone
Crystals grow, but
curve Nuclei form only
infinitely slowly
Under-saturation
(protein remains soluble; crystals dissolve)

Precipitant concentration (salt, PEG etc.)

26
 Metastable
Precipitation
Nucleates

Protein concentration
here
Nucleation
Crystal grows
Course of Sequesters protein
Crystallization [protein] drops

Experiment Crystal stops growing @

solubility curve
Start w/ soluble
protein
(undersaturated
or metastable) Expt incr. [protein], [precipitant]
Xtl grows again, until hits curve
[Precipitatant] Repeats as follows solubility curve
27
 CRYSTAL GROWTH
• Crystal growth is a diffusion process and a surface
phenomenon. Every crystal is surrounded by a layer of
liquid known as stagnant layer. From the bulk solution a
solute particle (molecule, atom or ion) diffuse through
this stagnant layer and then reaches the surface of the
crystal.

• This particles then organize themselves in the crystal

lattice. This phenomenon continues at the surface at a
slow rate. This process will happen if the bulk solution is
supersaturated.
 CRYSTALLIZATION PRINCIPLES
• Post nucleation process in which molecules in solution are added to the
surface of existing crystals
• The rate of mass deposition R during crystal growth is:
W: mass of crystals per volume of solvent;
(1) A : the surface area of crystals per volume of solvent;
kG : overall mass transfer coefficient (depends on temperature,
crystal size, hydrodynamic conditions, the presence of impurities);
g : usually 0 and 2.5

• Overall linear growth rate can also be expressed as:

(2)

L : characteristics single dimension of the crystal, such as length

• Crystal growth is a process that consists of two steps in series – diffusion and surface
30
integration
•
(3)

(4)
ci : concentration at the interface between the liquid
and solid phase; kd and kr : mass transfer coefficients

When the exponents are unity, combining Equation 1, 3, 4 gives

(5) Thus, if surface integration is very fast

compared with bulk diffusion, then kr >>
kd, and kG , kd.
 FACTORS AFFECTING THE CRYSTAL
• Presence of another substance in the mother liquor: Sodium chloride crystallized from
aqueous solutions produces cubic crystals. If sodium chloride is crystallized from a
solution containing a small amount of urea, the crystals obtained will have octahedral
faces. Both types of crystals belong to the cubic crystal form but differ in habit.
• Solvent: Griseofulvin crystallized out from acetone has different crystal habit than when
crystallized from benzene or chloroform.
• Rate of cooling: Acicular or needle-like crystals are produced when the solution is
cooled very slowly. Fluffy and small crystals are produced when the solution is cooled
very fast.
• Slow Evaporation: Slow Cooling:
- Time – faster crystallization is not as good as slow crystallization. Faster crystallization
higher chance of lower quality crystals
- Quality crystals grow best over time in near equilibrium conditions - - The longer the
time, the better the crystals
- Patience, patience, patience
 GROUP WORK
• Based on the extra notes last weeks, the website links below and also today
notes, put other important points in the Google Jamboard (20 minutes).
Also explain what happen to these graphs.
https://web.mit.edu/x-ray/cystallize.html
https://www.youtube.com/watch?v=nztV4w0DtOo

• Check out other group slides, leave comments to each group at least 2
comments per group (e.g. group 1, comment to group 2-5, for group 1, no
need to check the comments that given to your group, you all can resolve it
until next Monday) (10 minutes).

• 5 minutes before the end of this class, I will give another room id and
password.
YIELDS, HEAT AND MATERIAL BALANCES
 YIELDS, HEAT AND MATERIAL BALANCES

• The solution (mother liquor) and the solid crystals are in contact for enough time to
reach equilibrium. Hence, the mother liquor is saturated at the final temperature at
the final temperature of the process, and the final process, and the final
concentration of the solute in the solution can be obtained from the solubility curve.
• The yield can be calculated knowing the initial concentration of solute, the final
temperature, and the solubility at this temperature.
• In making the material balances, the calculations are straightforward when the
solute crystals are anhydrous. Simple water and solute material balances are made.
When the crystallizations are hydrated, some of the water in solution is removed with
the crystals as a hydrate.
• When the crystal growth rate is slow, considerable time is required to reach equilibrium,
especially for viscous solution or when not many crystal surface (at the bottom of
crystallizer) exposed to the supersaturated solution.
• The final mother liquor retains supersaturated and the actual yield is less than the
calculated from the solubility curve.
• When the crystals are in anhydrous, calculation is simple as the solid phase contains no
water.
• For the hydrate crystal, the water that accompanying the crystals is not available in
the solubility data.
• Therefore, to calculate the yields of hydrated solutes, all masses and concentrations
are expressed in terms of hydrated salt and free water.
 37

•
 EQUILIBRIUM SOLUBILITY

• In crystallization, equilibrium is attained when the solution or mother liquor is

saturated and can be represented by solubility curve.
• Solubility is a temperature dependent.
• See solubility curves (Fig. 27.2) for Mother liquor that retained in the dried solid mass
contaminates the product. The liquor can be separated from the crystals by filtering
or centrifuging and later washing with fresh solvent.
 39

•
1) KNO3 - solubility increases
rapidly with temperature,
2) NaCl - little change with
temperature
3) MnSO4.H2O in aqueous
solution – inverted solubility
curve i.e. solubility decreases
with increasing temperature.
 40

Example of solubility
sucrose in water
• During crystallization, the crystals are
grown from solutions with concentrations
higher than the saturation level in the
solubility curves.
• Above the supersaturation line, crystals
form spontaneously and rapidly, without
external initiating action (called as
spontaneous nucleation).
• Metastable region, the rate of initiation
of crystallization is slow.
• Below the saturation curve there is no
crystal growth, crystals instead dissolve.
 MASS AND ENERGY BALANCE
• Mass transfer occurs of a solute from the liquid solution to a pure solid
crystalline phase.
kg H2O evaporate

F kg hot solution S kg solution

Cooling Tc
X1 kg solute/ X2 kg solute/
100 kg H2O 100 kg H2O

C kg crystal

Mass balance :
Water balance : Input = Output
Solute balance : Input = Output
 EXAMPLE -1
• Yield of a Crystallization Process
• A salt solution weighing 10000 kg with 30 wt % Na2CO3 is cooled to 293 K (20 °C).
The salt crystallizes as the decahydrate. What will be the yield of Na2CO3•10H2O
crystals if the solubility is 21.5 kg anhydrous Na2CO3/100 kg of total water? Do this for
the following cases:

• (a) Assume that no water is evaporated.

• (b) Assume that 3% of the total weight of the solution is lost by evaporation of water
in cooling.

Process flow for crystallization

 SOLUTION
W kg H2O

10,000 kg solution S kg solution

Cooler and
30 % Na2CO3 crystallizer
21.5 kg Na2CO3 / 100 kg H2O

C kg crystals, Na2CO3˖10H2O
The molecular weights are 106.0 for Na2CO 3, 180.2 for 10H20, and 286.2 for Na2CO 3
•10H2O. The process flow diagram is shown in Fig. 3, with W being kg H2O evaporated,
S kg solution (mother liquor), and C kg crystals of Na2CO3 •10H2O.Making a material
balance around the dashed line box for water for part (a), where W = 0.
a) Material balance for H2O
100 180.2 (1)
0.7 10,000 = 𝑆 + 𝐶 +0
100 + 21.5 286.2

Material balance for Na2CO3

21.5 106.0
0.3 10,000 = 𝑆 + 𝐶 +0 (2)
100 + 21.5 286.2
Thus, C= 6370 kg of Na2CO3˖10H2O crystals and S=3630 kg solution
b) Material balance for H2O (For part (b), W = 0.03(10000) = 300 kg H2O)
100 180.2
0.7 10,000 = 𝑆 + 𝐶 + 300
100 + 21.5 286.2
Thus, C= 6630 kg of Na2CO3˖10H2O crystals and
S=3070 kg solution (since no salt is in the W stream)
 HEAT EFFECTS AND HEAT BALANCES IN
CRYSTALLIZATION
• When a compound whose solubility increases as temperature increases dissolves, there
is an absorption of heat, called the heat of solution – occurs when the solubility
decreases as the temperature increases
• At equilibrium the heat of crystallization is equal to the negative of the heat of solution
at the same concentration in solution.
• The enthalpy H1 of the entering solution at the initial temperature is read off the chart,
where H1 is kJ for the total feed. The enthalpy H2 of the final mixture of crystals and
mother liquor at the final temperature is also read off. If some evaporation occurs, the
enthalpy Hv of the water vapor is obtained from the steam tables. Then the total heat
absorbed q in kJ is

If q is positive, heat must be added to the system. If it is

negative, heat is evolved or given off.
 H2O, Tc, Hv

Hot solution Solute/solvent

Tf, H1 Tc, H3
• Tc

Total Heat Absorbed

Crystal, Tc, H2
q = (H2 + H3 + Hv) – H1

If q is positive, heat must be added to the system.

If it is negative, heat is evolved or given off.
 SUMMARY OF HEAT BALANCE
• Heat of Solution – absorption heat; when a
compound whose solubility increases as
temperature increases dissolves.
• In crystallization the opposite of dissolution occurs.
• At equilibrium the heat of crystallization is equal to
the negative of the heat of solution at the same
concentration in solution.
• The most satisfactory method of calculating heat
effects during a crystallization process is to use the
enthalpy-concentration chat.
 EXAMPLE 2
• A feed solution of 2268 kg at 327.6 K (54.4 °C) containing 48.2 kg MgSO4/100
kg total water is cooled to 293.2 K (20°C), where MgSO4•7H2O crystals are
removed. The solubility of the salt is 35.5 kg MgSO4/100 kg total water. The
average heat capacity of the feed solution can be assumed as 2.93 kJ/kg• K.
The heat of solution at 291.2 K (18 °C) is -13.31 x 103 kJ/kg mol MgSO4•7H2O.

Calculate the yield of crystals and make a heat balance to determine the
total heat absorbed, q, assuming that no water is vaporized.
 SOLUTION
• Making a water balance and a balance for MgSO4 using
equations similar to (13) and (14) in Example 1, C = 616.9
kg MgSO4•7H2O crystals and S = 1651.1 kg solution.
• To make a heat balance, a datum of 293.2 K (20°C) will
be used. The molecular weight of MgSO4•7H20 is 246.49.
The enthalpy of the feed is H1:
𝐻G = 2268 327.6 − 293.2 2.93 = 228 600 𝑘𝐽
 SOLUTION
• The heat of solution is -(13.31x103)/246.49 = -54.0 kJ/kg
crystals. Then the heat of crystallization is -(-54.0) = +54.0
kJ/kg crystals, or 54.0(616.9) = 33312 kJ. This assumes that
the value at 291.2 K is the same as at 293.2 K. The total
heat absorbed, q,
𝑞 = −226 800 − 33 312 = −261 912 𝑘𝐽
Since q is negative, heat is given off and must be removed.
NOTES
• MSMPR and equipments will be continue in next class.

• Drying will be introduced.

• Based on example 1 and 2, make your own questions and answer your own
questions (2 questions and 2 answers). Make notes about HOW to calculate
it, and how the equation will be applied. Please submit assignments before 5
pm on 20 April 2020, Monday. Submit in PDF format.
The application to make the PDF can be found in Apps Store.